Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103001860/sk1614sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103001860/sk1614Isup2.hkl |
CCDC reference: 208017
Compound (I) was prepared by the reaction of 4-nitrobenzenethiol with chloroacetic acid in the presence of triethylamine. Compound (I) was then oxidized using 30% aqueous hydrogen peroxide in a two-phase water/dichloromethane system, thus producing a mixture of (II) and (4-nitrophenylsulfinyl)acetic acid (III), from which (II) is readily separable by fractional crystallization from ethanol.
Compound (II) is monoclinic and the space group P21/c was uniquely assigned from the systematic absences. H atoms were treated as riding with O—H distances of 0.84 Å and C—H distances of 0.95 Å (aromatic) or 0.99 Å (CH2).
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).
C8H7NO5S | F(000) = 472 |
Mr = 229.22 | Dx = 1.628 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2124 reflections |
a = 13.7110 (7) Å | θ = 3.2–27.5° |
b = 7.3037 (3) Å | µ = 0.35 mm−1 |
c = 9.3537 (4) Å | T = 120 K |
β = 93.088 (2)° | Plate, colourless |
V = 935.33 (7) Å3 | 0.20 × 0.15 × 0.02 mm |
Z = 4 |
KappaCCD diffractometer | 2124 independent reflections |
Radiation source: Rotating Anode | 1588 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | h = −15→17 |
Tmin = 0.923, Tmax = 0.993 | k = −9→8 |
7061 measured reflections | l = −11→12 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0526P)2 + 0.33P] where P = (Fo2 + 2Fc2)/3 |
2124 reflections | (Δ/σ)max < 0.001 |
144 parameters | Δρmax = 0.79 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
C8H7NO5S | V = 935.33 (7) Å3 |
Mr = 229.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.7110 (7) Å | µ = 0.35 mm−1 |
b = 7.3037 (3) Å | T = 120 K |
c = 9.3537 (4) Å | 0.20 × 0.15 × 0.02 mm |
β = 93.088 (2)° |
KappaCCD diffractometer | 2124 independent reflections |
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997) | 1588 reflections with I > 2σ(I) |
Tmin = 0.923, Tmax = 0.993 | Rint = 0.056 |
7061 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.79 e Å−3 |
2124 reflections | Δρmin = −0.35 e Å−3 |
144 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.20558 (4) | 0.65399 (7) | 0.71021 (6) | 0.01954 (18) | |
O5 | 0.17742 (11) | 0.5651 (2) | 0.84711 (16) | 0.0220 (4) | |
C1 | 0.26862 (16) | 0.4852 (3) | 0.6118 (2) | 0.0183 (5) | |
C2 | 0.25576 (16) | 0.2990 (3) | 0.6365 (2) | 0.0205 (5) | |
C3 | 0.30936 (16) | 0.1737 (3) | 0.5611 (2) | 0.0195 (5) | |
C4 | 0.37325 (15) | 0.2402 (3) | 0.4635 (2) | 0.0186 (5) | |
N4 | 0.43007 (13) | 0.1080 (2) | 0.3832 (2) | 0.0208 (4) | |
O1 | 0.49132 (13) | 0.1682 (2) | 0.30462 (18) | 0.0303 (4) | |
O2 | 0.41335 (12) | −0.0562 (2) | 0.39842 (18) | 0.0263 (4) | |
C5 | 0.38575 (16) | 0.4248 (3) | 0.4366 (2) | 0.0206 (5) | |
C6 | 0.33308 (17) | 0.5492 (3) | 0.5133 (2) | 0.0216 (5) | |
C7 | 0.09633 (16) | 0.6606 (3) | 0.5930 (2) | 0.0205 (5) | |
C8 | 0.03000 (17) | 0.8074 (3) | 0.6458 (3) | 0.0238 (5) | |
O3 | 0.05419 (13) | 0.9127 (3) | 0.74139 (19) | 0.0369 (5) | |
O4 | −0.05533 (12) | 0.8082 (2) | 0.57336 (19) | 0.0294 (4) | |
H2 | 0.2111 | 0.2583 | 0.7039 | 0.016 (6)* | |
H3 | 0.3024 | 0.0458 | 0.5760 | 0.026 (7)* | |
H5 | 0.4293 | 0.4651 | 0.3675 | 0.023 (6)* | |
H6 | 0.3409 | 0.6770 | 0.4988 | 0.033 (7)* | |
H71 | 0.1135 | 0.6878 | 0.4938 | 0.040 (8)* | |
H72 | 0.0629 | 0.5404 | 0.5934 | 0.027 (7)* | |
H4 | −0.0906 | 0.8914 | 0.6049 | 0.080 (13)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0199 (3) | 0.0199 (3) | 0.0189 (3) | 0.0001 (2) | 0.0027 (2) | −0.0021 (2) |
O5 | 0.0233 (9) | 0.0261 (9) | 0.0167 (8) | −0.0001 (6) | 0.0015 (7) | 0.0008 (6) |
C1 | 0.0177 (11) | 0.0195 (11) | 0.0174 (11) | −0.0009 (8) | −0.0005 (9) | −0.0038 (9) |
C2 | 0.0198 (11) | 0.0242 (12) | 0.0177 (12) | −0.0047 (9) | 0.0034 (9) | 0.0003 (9) |
C3 | 0.0244 (12) | 0.0160 (10) | 0.0178 (11) | −0.0026 (8) | −0.0011 (9) | 0.0000 (9) |
C4 | 0.0191 (11) | 0.0199 (11) | 0.0167 (11) | 0.0014 (8) | −0.0013 (9) | −0.0032 (9) |
N4 | 0.0205 (10) | 0.0221 (10) | 0.0196 (10) | 0.0027 (8) | −0.0003 (8) | −0.0002 (8) |
O1 | 0.0337 (10) | 0.0279 (9) | 0.0307 (10) | 0.0043 (7) | 0.0160 (8) | 0.0019 (7) |
O2 | 0.0278 (9) | 0.0183 (9) | 0.0327 (10) | 0.0023 (6) | −0.0005 (7) | −0.0015 (7) |
C5 | 0.0189 (11) | 0.0228 (12) | 0.0204 (12) | −0.0043 (9) | 0.0038 (9) | 0.0012 (9) |
C6 | 0.0225 (12) | 0.0177 (11) | 0.0247 (13) | −0.0013 (8) | 0.0036 (10) | 0.0004 (9) |
C7 | 0.0214 (12) | 0.0238 (12) | 0.0163 (11) | 0.0016 (8) | 0.0021 (9) | −0.0004 (9) |
C8 | 0.0247 (13) | 0.0261 (12) | 0.0206 (12) | 0.0019 (9) | 0.0019 (10) | 0.0021 (10) |
O3 | 0.0361 (11) | 0.0425 (10) | 0.0313 (10) | 0.0134 (8) | −0.0047 (8) | −0.0128 (9) |
O4 | 0.0233 (9) | 0.0333 (10) | 0.0310 (10) | 0.0051 (7) | −0.0026 (8) | −0.0009 (8) |
S1—C1 | 1.789 (2) | C4—C5 | 1.384 (3) |
S1—C7 | 1.809 (2) | C4—N4 | 1.472 (3) |
S1—O5 | 1.5045 (16) | N4—O1 | 1.227 (2) |
C8—O3 | 1.212 (3) | N4—O2 | 1.231 (2) |
C8—O4 | 1.320 (3) | C5—C6 | 1.385 (3) |
C1—C6 | 1.392 (3) | C5—H5 | 0.95 |
C1—C2 | 1.392 (3) | C6—H6 | 0.95 |
C2—C3 | 1.390 (3) | C7—C8 | 1.507 (3) |
C2—H2 | 0.95 | C7—H71 | 0.99 |
C3—C4 | 1.387 (3) | C7—H72 | 0.99 |
C3—H3 | 0.95 | O4—H4 | 0.84 |
O5—S1—C1 | 107.08 (10) | O2—N4—C4 | 118.25 (18) |
O5—S1—C7 | 106.57 (10) | C4—C5—C6 | 118.2 (2) |
C1—S1—C7 | 96.54 (10) | C4—C5—H5 | 120.9 |
S1—C1—C2 | 121.26 (17) | C6—C5—H5 | 120.9 |
S1—C1—C6 | 116.79 (16) | C5—C6—C1 | 119.4 (2) |
C6—C1—C2 | 121.9 (2) | C5—C6—H6 | 120.3 |
C3—C2—C1 | 118.9 (2) | C1—C6—H6 | 120.3 |
C3—C2—H2 | 120.5 | C8—C7—S1 | 108.37 (15) |
C1—C2—H2 | 120.5 | C8—C7—H71 | 110.0 |
C4—C3—C2 | 118.25 (19) | S1—C7—H71 | 110.0 |
C4—C3—H3 | 120.9 | C8—C7—H72 | 110.0 |
C2—C3—H3 | 120.9 | S1—C7—H72 | 110.0 |
C5—C4—C3 | 123.4 (2) | H71—C7—H72 | 108.4 |
C5—C4—N4 | 118.19 (19) | O3—C8—O4 | 125.2 (2) |
C3—C4—N4 | 118.46 (19) | O3—C8—C7 | 123.2 (2) |
O1—N4—O2 | 123.77 (18) | O4—C8—C7 | 111.6 (2) |
O1—N4—C4 | 117.98 (18) | C8—O4—H4 | 109.5 |
C1—S1—C7—C8 | −175.84 (16) | C1—C2—C3—C4 | −0.3 (3) |
C7—S1—C1—C2 | −87.3 (2) | C2—C3—C4—C5 | −0.5 (3) |
C3—C4—N4—O1 | −175.0 (2) | C2—C3—C4—N4 | −179.92 (19) |
C5—C4—N4—O1 | 5.6 (3) | C5—C4—N4—O2 | −174.3 (2) |
S1—C7—C8—O3 | 7.3 (3) | C3—C4—N4—O2 | 5.2 (3) |
S1—C7—C8—O4 | −174.0 (2) | C3—C4—C5—C6 | 1.3 (3) |
O5—S1—C1—C6 | −155.66 (17) | N4—C4—C5—C6 | −179.29 (19) |
C7—S1—C1—C6 | 94.73 (19) | C4—C5—C6—C1 | −1.2 (3) |
O5—S1—C1—C2 | 22.4 (2) | C2—C1—C6—C5 | 0.4 (3) |
C6—C1—C2—C3 | 0.4 (3) | S1—C1—C6—C5 | 178.41 (17) |
S1—C1—C2—C3 | −177.53 (16) | O5—S1—C7—C8 | 74.12 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O5i | 0.84 | 1.81 | 2.648 (2) | 173 |
C5—H5···O1ii | 0.95 | 2.48 | 3.391 (3) | 160 |
C6—H6···O2iii | 0.95 | 2.40 | 3.286 (3) | 155 |
C7—H71···O3iv | 0.99 | 2.56 | 3.351 (3) | 137 |
C7—H71···O5iv | 0.99 | 2.46 | 3.289 (3) | 141 |
C7—H72···O3v | 0.99 | 2.47 | 3.206 (3) | 131 |
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, y+1, z; (iv) x, −y+3/2, z−1/2; (v) −x, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C8H7NO5S |
Mr | 229.22 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 13.7110 (7), 7.3037 (3), 9.3537 (4) |
β (°) | 93.088 (2) |
V (Å3) | 935.33 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.20 × 0.15 × 0.02 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | Multi-scan DENZO-SMN (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.923, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7061, 2124, 1588 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.110, 1.02 |
No. of reflections | 2124 |
No. of parameters | 144 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.79, −0.35 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).
S1—C1 | 1.789 (2) | C8—O3 | 1.212 (3) |
S1—C7 | 1.809 (2) | C8—O4 | 1.320 (3) |
S1—O5 | 1.5045 (16) | ||
O5—S1—C1 | 107.08 (10) | S1—C1—C2 | 121.26 (17) |
O5—S1—C7 | 106.57 (10) | S1—C1—C6 | 116.79 (16) |
C1—S1—C7 | 96.54 (10) | O1—N4—O2 | 123.77 (18) |
C1—S1—C7—C8 | −175.84 (16) | C5—C4—N4—O1 | 5.6 (3) |
C7—S1—C1—C2 | −87.3 (2) | S1—C7—C8—O3 | 7.3 (3) |
C3—C4—N4—O1 | −175.0 (2) | S1—C7—C8—O4 | −174.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O5i | 0.84 | 1.81 | 2.648 (2) | 173 |
C5—H5···O1ii | 0.95 | 2.48 | 3.391 (3) | 160 |
C6—H6···O2iii | 0.95 | 2.40 | 3.286 (3) | 155 |
C7—H71···O3iv | 0.99 | 2.56 | 3.351 (3) | 137 |
C7—H71···O5iv | 0.99 | 2.46 | 3.289 (3) | 141 |
C7—H72···O3v | 0.99 | 2.47 | 3.206 (3) | 131 |
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, y+1, z; (iv) x, −y+3/2, z−1/2; (v) −x, y−1/2, −z+3/2. |
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In (4-nitrophenylsulfanyl)acetic acid, O2NC6H4SCH2COOH, (I), the molecules are linked by paired O—H···O hydrogen bonds into dimers. These are further linked by C—H···O hydrogen bonds to form molecular ladders, which are themselves weakly linked into sheets by aromatic π–π-stacking interactions (Glidewell et al., 2002). Oxidation of this acid at the S atom to (4-nitrophenylsulfinyl)acetic acid, O2NC6H4S(O)CH2COOH, (II), which contains three potential acceptors of hydrogen bonds [O═C, O═S and O═N], provides many other possibilities for the supramolecular aggregation, including the possible formation of O—H···O═S and C—H···O═S hydrogen bonds. Here we report the molecular and supramolecular structure of (II) (Fig. 1), which contains, in addition to an O—H···O═S hydrogen bond, a rather unusual three-centre C—H···(O)2 hydrogen bond in which the two oxygen acceptors are bonded to C and S, respectively.
The single O—H···O hydrogen bond in (II) generates continuous chains, rather than the usual R22(8) dimer so characteristic of carboxylic acids. The carboxyl atom O4 in the molecule at (x, y, z) acts as hydrogen-bond donor to the sulfoxide atom O5 in the molecule at (-x, 0.5 + y, 1.5 − z), so producing a C(6) chain running parallel to the [010] direction and generated by the 21 screw axis along (0, y, 3/4). Three C—H···O hydrogen bonds link these C(6) chains into sheets. Atom C5 at (x, y, z) acts as hydrogen-bond donor to nitro O1 at (1 − x, 0.5 + y, 0.5 − z), so producing a C(5) chain that is also parallel to [010] but this time is generated by the 21 screw axis along (1/2, y, 1/4). The combination of these two chain motifs suffices to generate a sheet parallel to (101) that is reinforced by a second C—H···O hydrogen bond. Atom C6 at (x, y, z) acts as donor to the nitro atom O2 at (x, 1 + y, z), so generating by translation a C(6) chain that is again parallel to [010]. The (101) sheet thus consists of alternating strips of edge-fused R33(12) rings, which are generated by screw axes at (1/2, y, 1/4) and translation-related sites, and similar strips of edge-fused R33(22) rings, which are generated by screw axes along (0, y, 3/4) and translation-related sites (Fig. 2). Further reinforcement of the sheets is provided by another type of C—H···O hydrogen bond, in which the methylene C atom acts as the donor. Atom C7 in the molecule at (x, y, z) acts as donor, via H72, to the carboxyl atom O3 in the molecule at (-x, −0.5 + y, 1.5 − z), so producing a C(4) chain generated by the 21 screw axis along (0, y, 3/4) (Fig. 3).
Two (101) sheets pass through each unit cell, and adjacent sheets are linked by a chain along [001] that is generated by a nearly planar three-centre C—H···(O)2 hydrogen bond. The sum of the angles at H is 357°. Atom C7 in the molecule at (x, y, z) acts, via H71, as hydrogen-bond donor to both carboxyl atom O3 and sulfoxide atom O5, both in the molecule at (x, 1.5 − y, −0.5 + z), so producing a C(4) C(4)[R21(6)] chain of rings (Fig. 3) running parallel to [001] and generated by the c-glide plane at y = 0.75. This chain contains the uncommon supramolecular synthon A (see Scheme), in which a C—H bond acts as donor concurrently to carboxyl and sulfoxide O atoms.
The combination of the (101) sheets and the [001] chains is sufficient to generate a single three-dimensional framework. However, in contrast to the supramolecular structure of (I), there are no π–π- stacking interactions in (II). Note that while the sulfoxide O in (II) participates in the O—H···O hydrogen bond in preference to the other potential acceptors in the carboxyl and nitro groups, the C—H···O hydrogen bonds utilize all three types of O acceptor (Table 2).
Within the molecule of (II), the lengths of the three bonds to S (Table 1) are all typical of their types (Allen et al., 1987). The two C—O distances in the carboxyl group are entirely consistent with the location of the acid H atom as deduced from a difference map. Although the coordination round the S atom is sharply pyramidal, the torsion angles C1—S1—C7—C8 and S1—C7—C8—O3/)4 indicate that the molecular fragment running from C1 to the carboxyl O atoms O3 and O4 is nearly planar. By contrast, the torsion angle C7—S1—C1—C2 indicates that the aryl ring is nearly orthogonal to the plane of the side chain, while the dihedral angle between the nitro group and the aryl ring is only 5.2 (2) Å.